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The title compound, C14H24N2O4, is an intermediate in the synthesis of the corresponding heterocyclic compounds. The mol­ecule lies about a twofold axis and has a `twist' conformation; it adopts the Z,Z configuration, which is shown to be governed mainly by intramolecular hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104000241/ty1002sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104000241/ty1002Isup2.hkl
Contains datablock I

CCDC reference: 235335

Comment top

The condensation reaction of ethylenediamine with ethyl acetoacetate, catalyzed by various Friedel-Crafts-type catalysts, gives the open chain compound (I) (Moazzam et al., 1988). However, we found that the reaction occurs easily without any catalyst and yields a crystalline product that was originally thought to have the structure of (I). However, 1H NMR suggested that there are two vinyl H atoms (δ 4.43, s) and two H atoms on the N (δ 8.59, s), and that the structure is thus in fact (II) (Costes & Laurent, 1988). \sch

Although structure (II) is strongly supported by 1H NMR spectroscopy, there are still some questions regarding its conformation and configuration. In addition to verifying structure (II), X-ray analysis of the compound has now been undertaken and the results are presented here (Fig. 1).

The ethylenediamine structural unit in this molecule adopts a low-energy gauche conformation with respect to the central C7—C7A bond, which is very similar to 1,2-ethanediamine (Burgess et al., 1976; Marstokk & Mοllendal, 1978). The molecule adopts a `twist' conformation, with an N1—C7—C7A—N1A torsion angle of 66°, and the C4C5 bond is in the (Z,Z) configuration.

The N1—C5 bond length of 1.342 (4) Å is shorter than the standard N—C experimental bond length of 1.469 Å (Lice, 1957). This large difference is considered to be the result of ππ conjugation between the N atom and the CC bond. Conversely, the C3O2 bond [1.222 (4) Å] is longer than that in other derivative compounds [e.g. 1.199 (3) Å; Balsamini et al., 1992]. The O2—C3—C4—C5 torsion angle is −1.7°, indicating that the ππ conjugation is spread between the CC bond and the CO (ester) bond.

Another interesting characteristic of (II) is its (Z,Z) configuration, which is probably caused and stabilized by intramolecular N—H···OC hydrogen bonds (Fig.2 and Table 2) (Jeffrey, 1997).

Experimental top

Diethyl (Z,Z)-3,3'-(1,2-ethanediyldinitrilo)dibut-2-enoate was prepared by the condensation of 1,2-diaminoethane and ethyl acetoacetate (molar ratio 1:2) in alcohol at room temperature. The product was recrystallized from dichloromethane (yield 92%, m.p. 399–401 K). Spectroscopic analysis: 1H NMR (300 MHz, CDCl3, δ, p.p.m.): 8.59 (s, 2H, NH), 4.43 (s, 2H, CH), 4.02 (q, J = 15 Hz, 4H, ethyl CH2), 3.31 (d, J = 6 Hz, 4H, ethylene CH2), 1.86 (s, 6H, CH3), 1.19 (t, J = 15, 6H, ethyl CH3).

Refinement top

H atoms were constrained to their parent atoms using a riding model, with C—H distances in the range 0.93–0.96 Å and N—H distances of 0.86 Å, and with Uiso(H) = 1.2 or 1.5 times Ueq of the parent atom. Please check added text.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (II), showing the atom-labelling scheme and with 40% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A packing diagram for (II), viewed along the b axis.
Diethyl (Z,Z)-3,3'-(1,2-ethanediyldinitrilo)dibut-2-enoate top
Crystal data top
C14H24N2O4Dx = 1.253 Mg m3
Mr = 284.35Melting point = 399–401 K
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 11.505 (2) ÅCell parameters from 1735 reflections
b = 10.540 (2) Åθ = 2.7–25.8°
c = 13.471 (3) ŵ = 0.09 mm1
β = 112.66 (3)°T = 293 K
V = 1507.4 (6) Å3Block, colourless
Z = 40.30 × 0.20 × 0.20 mm
F(000) = 616
Data collection top
Bruker SMART CCD area-detector
diffractometer
1325 independent reflections
Radiation source: fine-focus sealed tube1147 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
ω scansθmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1013
Tmin = 0.973, Tmax = 0.982k = 1211
3026 measured reflectionsl = 1514
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.076Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.206H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0925P)2 + 4.2899P]
where P = (Fo2 + 2Fc2)/3
1325 reflections(Δ/σ)max < 0.001
91 parametersΔρmax = 0.50 e Å3
0 restraintsΔρmin = 0.49 e Å3
Crystal data top
C14H24N2O4V = 1507.4 (6) Å3
Mr = 284.35Z = 4
Monoclinic, C2/cMo Kα radiation
a = 11.505 (2) ŵ = 0.09 mm1
b = 10.540 (2) ÅT = 293 K
c = 13.471 (3) Å0.30 × 0.20 × 0.20 mm
β = 112.66 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1325 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1147 reflections with I > 2σ(I)
Tmin = 0.973, Tmax = 0.982Rint = 0.032
3026 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0760 restraints
wR(F2) = 0.206H-atom parameters constrained
S = 1.07Δρmax = 0.50 e Å3
1325 reflectionsΔρmin = 0.49 e Å3
91 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.1214 (2)0.1390 (2)0.02196 (17)0.0414 (6)
O20.0420 (2)0.3379 (2)0.00038 (17)0.0434 (7)
N10.0909 (2)0.4645 (2)0.1940 (2)0.0356 (7)
H1A0.06990.47350.12580.043*
C10.1345 (3)0.0067 (3)0.1154 (3)0.0476 (9)
H1B0.11170.00250.19150.071*
H1C0.09950.06220.08930.071*
H1D0.22460.00580.07960.071*
C20.0842 (3)0.1302 (3)0.0931 (3)0.0431 (8)
H2A0.11870.20060.11920.052*
H2B0.00690.13220.12870.052*
C30.0976 (3)0.2514 (3)0.0603 (2)0.0358 (7)
C40.1481 (3)0.2512 (3)0.1761 (2)0.0357 (7)
H4A0.18640.17740.21150.043*
C50.1429 (3)0.3534 (3)0.2370 (2)0.0338 (7)
C60.2051 (3)0.3430 (3)0.3576 (2)0.0422 (8)
H6A0.19370.42090.38970.063*
H6B0.29340.32700.37810.063*
H6C0.16760.27450.38190.063*
C70.0665 (3)0.5711 (3)0.2515 (2)0.0349 (7)
H7A0.08070.64950.22010.042*
H7B0.12560.56850.32580.042*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0543 (14)0.0363 (12)0.0343 (12)0.0070 (10)0.0179 (10)0.0005 (9)
O20.0535 (14)0.0387 (13)0.0376 (12)0.0104 (10)0.0170 (11)0.0035 (10)
N10.0400 (14)0.0383 (14)0.0309 (13)0.0051 (11)0.0162 (11)0.0027 (10)
C10.057 (2)0.045 (2)0.0422 (19)0.0065 (16)0.0207 (15)0.0047 (15)
C20.0520 (19)0.0411 (18)0.0362 (17)0.0052 (15)0.0171 (14)0.0012 (14)
C30.0388 (16)0.0328 (16)0.0392 (17)0.0009 (13)0.0188 (13)0.0005 (13)
C40.0377 (15)0.0356 (16)0.0344 (16)0.0051 (13)0.0145 (12)0.0033 (12)
C50.0316 (14)0.0369 (17)0.0342 (16)0.0020 (12)0.0141 (12)0.0038 (12)
C60.0506 (18)0.0424 (18)0.0326 (17)0.0048 (15)0.0151 (14)0.0024 (13)
C70.0399 (16)0.0301 (15)0.0367 (16)0.0006 (12)0.0169 (13)0.0002 (12)
Geometric parameters (Å, º) top
O1—C31.362 (4)C2—H2B0.9700
O1—C21.443 (4)C3—C41.439 (4)
O2—C31.222 (4)C4—C51.370 (4)
N1—C51.342 (4)C4—H4A0.9300
N1—C71.452 (4)C5—C61.505 (4)
N1—H1A0.8600C6—H6A0.9600
C1—C21.501 (4)C6—H6B0.9600
C1—H1B0.9600C6—H6C0.9600
C1—H1C0.9600C7—C7i1.515 (6)
C1—H1D0.9600C7—H7A0.9700
C2—H2A0.9700C7—H7B0.9700
C3—O1—C2116.3 (2)C5—C4—C3123.7 (3)
C5—N1—C7126.2 (3)C5—C4—H4A118.1
C5—N1—H1A116.9C3—C4—H4A118.1
C7—N1—H1A116.9N1—C5—C4122.9 (3)
C2—C1—H1B109.5N1—C5—C6118.5 (3)
C2—C1—H1C109.5C4—C5—C6118.5 (3)
H1B—C1—H1C109.5C5—C6—H6A109.5
C2—C1—H1D109.5C5—C6—H6B109.5
H1B—C1—H1D109.5H6A—C6—H6B109.5
H1C—C1—H1D109.5C5—C6—H6C109.5
O1—C2—C1107.1 (3)H6A—C6—H6C109.5
O1—C2—H2A110.3H6B—C6—H6C109.5
C1—C2—H2A110.3N1—C7—C7i112.7 (2)
O1—C2—H2B110.3N1—C7—H7A109.0
C1—C2—H2B110.3C7i—C7—H7A109.0
H2A—C2—H2B108.6N1—C7—H7B109.0
O2—C3—O1121.9 (3)C7i—C7—H7B109.0
O2—C3—C4127.4 (3)H7A—C7—H7B107.8
O1—C3—C4110.7 (3)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O20.862.142.787 (3)132

Experimental details

Crystal data
Chemical formulaC14H24N2O4
Mr284.35
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)11.505 (2), 10.540 (2), 13.471 (3)
β (°) 112.66 (3)
V3)1507.4 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.30 × 0.20 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.973, 0.982
No. of measured, independent and
observed [I > 2σ(I)] reflections
3026, 1325, 1147
Rint0.032
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.076, 0.206, 1.07
No. of reflections1325
No. of parameters91
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.50, 0.49

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.

Selected geometric parameters (Å, º) top
O1—C31.362 (4)C3—C41.439 (4)
O2—C31.222 (4)C4—C51.370 (4)
N1—C51.342 (4)
C5—N1—C7126.2 (3)N1—C5—C4122.9 (3)
O2—C3—C4127.4 (3)N1—C5—C6118.5 (3)
O1—C3—C4110.7 (3)C4—C5—C6118.5 (3)
C5—C4—C3123.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O20.862.142.787 (3)132
 

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